CN103011136A - Method for synthetizing graphene film - Google Patents
Method for synthetizing graphene film Download PDFInfo
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- CN103011136A CN103011136A CN2011102876219A CN201110287621A CN103011136A CN 103011136 A CN103011136 A CN 103011136A CN 2011102876219 A CN2011102876219 A CN 2011102876219A CN 201110287621 A CN201110287621 A CN 201110287621A CN 103011136 A CN103011136 A CN 103011136A
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Abstract
The invention discloses a method for preparing a graphene film, comprising the steps of activating carbon atoms in carbon-containing gaseous carbon source, solid carbon source and liquid carbon source or a mixed carbon source material of any two or more than two of the carbon sources by adopting the technical methods of energy particles such as laser beam, electron beam, radio frequency beam, radial, photon, neutron beam, ion beam, plasma and the like; and forming the graphene film on a substrate. The method for producing the carbon atoms needed in the graphene film synthetizing is different from a conventional method and has the advantages that the method has great selectivity, and has no special requirement on the carbon source material and no special requirement on the substrate; the graphene film can be synthetized on the substrate which has the catalytic function and can be directly synthetized on the semiconductor or insulator substrate which does not have the catalytic function; and the formed graphene film is easily controlled in the aspects of the number of layers, structure and size and suitable for manufacturing high-performance photoelectronic devices on a large scale.
Description
Technical field
The present invention relates to graphene film, relate in particular to a kind of method of synthesizing graphite alkene film.
Background technology
Graphene is that mono-layer graphite is otherwise known as by the former molecular two-dirnentional structure material of cellular monolayer carbon; On physical property, it has been generally acknowledged that the material that Graphene is piled up more than ten layers is exactly the graphite of three-dimensional structure, carbon nanotube is the monodimension nanometer material that is rolled into tubbiness by Graphene.Graphene has remarkable two-dimentional electricity, optics, calorifics, mechanical property and chemical stability, and the crystallography quality of its unique two-dirnentional structure and excellence is so that it has important practical value in fields such as supper-fast micro-nano opto-electronic device, radio-frequency devices, clear energy sources and various kinds of sensors.Such as, electronics is followed relativistic quantum mechanics in Graphene, there is not rest mass, ultraspeed operation with 1/300 light velocity, show unusual room temperature quantum hall effect and ballistic transport phenomenon, can prepare room temperature ballistic transport transistor, be regarded as the important foundation novel material of Future Information nano-device; Graphene electric transmission speed is 150 times of silicon, is expected to supper-fast computer and radio-frequency devices that the speed of preparing reaches megahertz; The susceptibility of the unit molecule degree of Graphene is expected to be used widely such as fields such as gas sensor and biosensors at various sensors; Graphene has the optical characteristics of 2.3% photoabsorption, makes it can be for the preparation of supper-fast photo-detector and mode locked laser.On the other hand, because extremely low optical absorption characteristics, so that Graphene both can be used for preparing opto-electronic device, transparency electrode such as photodiode and solar cell etc., thereby replace cost costliness, resource scarcity, the not collapsible ITO nesa coating take indium as main component, also can be used for preparing ultracapacitor and lithium ion battery; Effciency of energy transfer based on the solar battery of Graphene is expected to reach 24%.
The preparation method of graphene film comprises mechanically peel method [K.S.Novoselov, et al.Science 306,666 (2004)], solution stripping method [X.L.Li, et al.Science 319,1229 (2008)], the oxidation-reduction method [D.A.Dikin of graphite, et al.Nature 448,457 (2007); Z.S.Wu, et al.Carbon 47,493 (2009)], the silicon carbide thermal decomposition method [C.Berger, et al.Science 312,1191 (2006); A.Tzalenchuk, et al.Nature Nanotechnol 5,186 (2010)], chemical Vapor deposition process (CVD) [C.A.Di, et al.Adv.Mater.20,3289 (2008); A.Reina, et al.Nano Lett.9,30 (2009); K.S.Kim, et al.Nature 457,706 (2009)], carbon segregation method (segregation) etc.Wherein the shape of the graphene film prepared of the oxidation reduction process of mechanically peel method, solution stripping method and graphite all is random basically, and the number of plies of graphene film and size are difficult to control; Although the mechanically peel method can produce the graphene film of perfect lattice, only be adapted to fundamental research, be not suitable for large-scale application.The silicon carbide thermal decomposition method is a kind of method of solid-state carbon source growing graphene film, its basic step is included under the ultrahigh vacuum(HHV), pyroprocessing silicon carbide with about 1400 ℃, Siliciumatom is evaporated and allow carbon atom form graphene film at silicon carbide, this method requires very high, very harsh to preparation condition, and is difficult to obtain the single uniform graphene film of the number of plies.CVD and carbon segregation method can big area synthesizing graphite alkene films, and can control preferably to a certain extent the number of plies of graphene film, be adapted to large-scale application, but synthesis temperature are generally about 1000 ℃.Like this, because the CVD method is synthesizing graphite alkene film on the metal substrate of catalysis usually, during the practical application graphene film, must transfer on other target substrate such as the insulating substrate at the synthetic big area graphene film of metal substrate and just can use graphene film; Also there is very large difficulty at present big area transfer graphene film.Therefore, if there is technological method graphene film can be grown directly upon on the substrate such as insulating substrate or semiconducter substrate that is fit to the graphene film particular application technology, to omit transfer step, also can avoid the variation of the graphene film texture quality that causes because of transfer process, the field that this will greatly accelerate the development of Graphene technology and widen practical application.
Recently, the existing employing without the CVD method synthesizing graphite alkene film of metal catalytic layer or the bibliographical information of similar graphene film material is as at Al
2O
3Upper synthesizing graphite alkene film [M.A.Fanton, et al.ACS Nano, Online Computer File, 2011, DOI:10.1021/nn202643]; The graphene film sheet of synthesis of nano size on MgO [M.H.Ruemmeli, et al.arXiv.org, e-Print Archive, Condensed Matter, Pages:1-13, arXiv:1103.0497v1, Preprint, 2011]; At quartz, Si (100) and SiO
2Having synthesized size on the substrate is thin film containing carbon [the Kim Ki-Bum of the similar grapheme material of 100-200 nanometer, et al., J.Phy.Chem.C 115,14488 (2011)], be approximately the film that the graphene film sheet of 10 nanometers forms by size in that multiple substrate is synthetic; Without the required synthesis temperature of chemical Vapor deposition process (CVD) the synthesizing graphite alkene film of metal catalytic layer very high (being higher than 1400 ℃), the graphene film small-sized (10-200 nanometer) that perhaps synthesizes.
The contriver of this patent discloses methods such as adopting sputter graphite material has been deposited on the metal catalytic layer and the patent of synthesizing graphite alkene film process [CN101913598A]; Adopt similarly method, Ruoff etc. are depositing carbon film on metal copper sheet catalytic substrate, then carries out the synthetic single-layer graphene [R.S.Ruoff, et al., ACS Nano DOI:10.1021/nn202802x] of anneal; But above-mentioned technological method just has synthesizing graphite alkene film on the metal substrate of catalytic activity with the solid carbon deposition of material.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of simple technological method that is suitable for synthetic graphite film on any target substrate is provided; Particularly, the active atoms of carbon that utilize to produce or carbonaceous active group can be on the semi-conductor that does not have catalysis and insulator substrates the method for the graphene film of large area deposition.For this reason, the present invention by the following technical solutions: adopt the energy particle technological method to produce active atoms of carbon or carbonaceous active group in two or more mixed carbon source material arbitrarily from the solid-state carbon source, liquid carbon source, gaseous carbon source material or the aforementioned carbon source that contain carbon; The active atoms of carbon that produces or carbonaceous active group be deposited on the substrate with catalytic activity or have on the substrate of catalytic activity and form graphene film.
Described energy particle technological method comprises radio frequency processing, laser treatment, electron beam treatment, neutron beam processing, Ion Beam Treatment, Cement Composite Treated by Plasma, microwave treatment, Irradiation, UV treatment or infra red treatment.
The described substrate that does not have catalytic activity comprises semi-conductor or insulating material, as but be not limited to Si, GaN, Ge, ZnO, CuO, InAs, GaAs, SiO
2, Al
2O
3, HfO
2, BN, SiC, SiN
x, MgO, GeS, BaF
2, MgF
2, LaF
3, GaF
2, GaP, InP, LiF, InSb, BaTiO
3, LiNbO
3, LaAlO
3, NdGaO
3, SrTiO
3, LaAlO
3, LiGaO
2, LiTaO
3, YAlO
3, YVO
4, ZnS, ZnSe, ZnTe, sapphire, mica, polymer poly ethylene glycol terephthalate (PET) etc.
Described substrate with catalytic activity comprises Ni, Pt, Co, Fe, Al, Cr, Mg, Mn, Rh, Ta, Ti, W, U, Zr, V, Pd, Ru, Ir, Re, TiC, HfC, WC, LaB
6Or a kind of or its arbitrary combination of polycrystalline copper.
Described active atoms of carbon refers to form the carbon atom of Graphene, and described carbonaceous active group refers to the group with carbonium ion or carbanion.
The number of plies of the graphene film that forms at described substrate is 1 layer to 100 layers, is preferably 1 layer to 10 layers, and optimum is 1 layer to 3 layers.
The substrate surface feature of graphene film growth is including, but not limited to having the substrate of certain regular pattern, single crystalline substrate such as the surface atom ordered arrangement, the polycrystalline substrate of surface tissue short range order, the amorphous substrate that surfacing is smooth, there is the substrate of atomic steps on the surface, there is the substrate of functional group on the surface, there is the substrate of nanostructure etc. on the surface, such as Si (100) surface, the atomic steps on GaN (111) surface, the Si of surface convex-concave, the Si substrate that process through HF on the surface, the alkylating Si substrate in surface, Au (111) surface, the Au substrate that process through mercapto functional group on the surface, the surface is through UV-O
3The SiO that processes
2Substrate, smooth smooth polymer poly ethylene glycol terephthalate (PET) substrate etc.
The structure of the short range order of described polycrystalline substrate surface refers to that the length range of ordered structure is greater than 5 nanometers.
The smooth smooth surface of described amorphous substrate refers to that surfaceness is less than the surface of 100 nanometers.
It is the nanostructure of the nano wire, nano dot, nanotube etc. of 0.5 nanometer～100 nanometers that nanostructure on the described substrate refers to have at least the size of one dimension.
Describedly contain that the gaseous carbon source of carbon, solid-state carbon source, liquid carbon source material or mixed carbon source material refer to adopt described technological method or means and the material that can discharge easily the carbon elements of carbon atom or carbonaceous active group, comprise alkane such as methane etc., alkene such as ethene etc., alkynes such as acetylene etc., aromatic hydrocarbon such as benzene etc., alcohol is such as ethanol etc., ketone such as acetone etc., the material of the carbon containings such as polymkeric substance, graphite, agraphitic carbon, soccerballene, carbon pipe, but be not limited to above material.
To be the technological method that adopts energy particle with active atoms of carbon or carbonaceous active group produce from the carbon source materials of carbon containing the method for preparing graphene film of the present invention and direct large area deposition graphene film on target substrate; Can be on any substrate, particularly can be on the semi-conductor that does not have catalytic activity and insulator substrates direct synthesizing graphite alkene film.On the required carbon atom technological method of synthesizing graphite alkene film, technological method of the present invention is different from the methods such as conventional chemical Vapor deposition process (CVD) and carbon segregation, the production method of the carbon atom that the synthesizing graphite alkene film is required has very large selectivity, and required carbon source material is not had special requirement; The present invention can directly directly prepare graphene film on semi-conductor or insulator substrates, since do not need with graphene film from the substrate-transfer of synthesizing graphite alkene film to the substrate that uses, this can keep the performance of the graphene film that synthesized not to be changed, for realizing that the application of graphene film in the semi-conductor photoelectronic field has very important realistic meaning, this is with the decrease cost like this; The thickness of graphene film, structure, size are controlled easily; Be applicable to make on a large scale high performance opto-electronic device.
Description of drawings
Fig. 1 is the synoptic diagram that the present invention prepares graphene film: comprise that (a) adopts the energy particle technological method to produce active atoms of carbon or carbonaceous active group in two or more mixed carbon source material arbitrarily from the gaseous carbon source, liquid carbon source, solid-state carbon source or the aforementioned carbon source that contain carbon, (b) active atoms of carbon or carbonaceous active group are deposited on the substrate and form graphene film.
Fig. 2 has the substrate of regular pattern for some: (a) single crystalline substrate of surface atom ordered arrangement, the atomic steps surperficial such as Si (100), that GaN (111) is surperficial, Au (111) surface etc.; (b) has the substrate of the pattern of convex-concave, such as Si, the PET etc. of surperficial convex-concave; (c) surface has the substrate of functional group, and the Au substrate that process through mercapto functional group on Si substrate, surperficial alkylating Si substrate, the surface of processing through HF such as the surface, surface are through UV-O
3The SiO that processes
2Substrate etc.; (d) surface has the substrate of nanostructure.
Fig. 3 is the scanning electron microscope image at single crystalline Si Grown graphene film.
Fig. 4 is for to transfer to SiO at polycrystalline copper Grown single-layer graphene
2Auger electron collection of illustrative plates on the substrate.
Shown in the figure: 1, energy particle generator; 2, the gaseous carbon source, liquid carbon source or the solid-state carbon source that contain carbon atom; 3, active atoms of carbon or carbonaceous active group; 4, substrate; 5, graphene film; 6, the orderly atomic structure of single crystalline substrate; 7, the functional group on the substrate; 8, the nanostructure on the substrate.
Embodiment
As shown in Figure 1, the method of synthesizing graphite alkene film is to adopt the energy particle technological method to produce active atoms of carbon or carbonaceous active group in two or more mixed carbon source material arbitrarily from the gaseous carbon source, liquid carbon source, solid-state carbon source or the aforementioned carbon source that contain carbon, the active atoms of carbon that produces or carbonaceous active group is deposited on the substrate with catalytic activity or has on the substrate of catalytic activity to form graphene film.
Described energy particle technological method includes but not limited to radio frequency processing, laser treatment, electron beam treatment, neutron beam processing, Ion Beam Treatment, Cement Composite Treated by Plasma, microwave treatment, X ray processing, alpha-ray processing, β Irradiation, gamma-rays processing, UV treatment, infra red treatment or thermal radiation processing.
Described active atoms of carbon refers to form the carbon atom of Graphene; Described carbonaceous active group refers to the group with carbonium ion or carbanion.
Described substrate comprises it being the substrate with catalytic activity or weak catalytic activity, such as Ni, Pt, Co, Fe, Al, Cr, Cu, Mg, Mn, Rh, Ta, Ti, W, U, Zr, V, Pd, Ru, Ir, Re, TiC, HfC, WC, LaB
6Or a kind of or its arbitrary combination of polycrystalline copper, also can be substrate such as semi-conductor or the insulator substrates with catalytic activity, including, but not limited to Si, GaN, Ge, ZnO, CuO, InAs, GaAs, SiO
2, Al
2O
3, HfO
2, BN, SiC, SiN
x, MgO, GeS, BaF
2, MgF
2, LaF
3, GaF
2, GaP, InP, LiF, InSb, BaTiO
3, LiNbO
3, LaAlO
3, NdGaO
3, SrTiO
3, LaAlO
3, LiGaO
2, LiTaO
3, YAlO
3, YVO
4, ZnS, ZnSe, ZnTe, sapphire, mica, polymer poly ethylene glycol terephthalate (PET) etc.
The substrate surface feature of graphene film growth is including, but not limited to having the substrate of certain regular pattern, single crystalline substrate such as the surface atom ordered arrangement, the polycrystalline substrate of surface tissue short range order, the amorphous substrate that surfacing is smooth, there is the substrate of atomic steps on the surface, there is the substrate of functional group on the surface, there is the substrate of nanostructure etc. on the surface, such as Si (100) surface, the atomic steps on GaN (111) surface, the Si of surface convex-concave, the Si substrate that process through HF on the surface, the alkylating Si substrate in surface, Au (111) surface, the Au substrate that process through mercapto functional group on the surface, the surface is through UV-O
3The SiO that processes
2Substrate, smooth smooth polymer poly ethylene glycol terephthalate (PET) substrate etc.
The structure of the short range order of described polycrystalline substrate surface refers to that the length range of ordered structure is greater than 5 nanometers.
The smooth smooth surface of described amorphous substrate refers to that surfaceness is less than the surface of 100 nanometers.
Nanostructure on the described substrate refers to that its size that has one dimension at least is the nanostructure of nano wire, nano dot, nanotube of 0.5 nanometer～100 nanometers etc.
Describedly be that the number of plies of the graphene film that forms at substrate is 1 layer to 100 layers, be preferably 1 layer to 10 layers, optimum is 1 layer to 3 layers.
The described gaseous carbon source of carbon, solid-state carbon source, liquid carbon source material or its mixed carbon source of containing refers to contain material by carbon atom, optimum material for producing active atoms of carbon or active atoms of carbon group by method or the means of described generation active atoms of carbon or carbonaceous active group, comprise alkane such as methane etc., alkene such as ethene etc., alkynes such as acetylene etc., aromatic hydrocarbon such as benzene etc., alcohol is such as ethanol etc., ketone such as acetone etc., the material of the carbon containings such as polymkeric substance, graphite, agraphitic carbon, soccerballene, carbon pipe, but be not limited to above material.
Embodiment 1: at Si (100) Grown graphene film
May further comprise the steps: N-shaped Si (100) is sent to supervacuum chamber, at 600 ℃ of thermal treatment 300min, then is warming up to 1000 ℃ of thermal treatments 3 times, each 0.5min, thus obtain clean Si (100) surface; Keep the temperature of substrate Si (100) at 800 ℃, toward the logical H of supervacuum chamber
2With C
2H
4Mixed gas, and with the electron beam that comes from electron beam gun with C
2H
4Ionization became the active atoms of carbon group, Si (100) Grown graphene film 5 minutes; At last 20 ℃/minute of underlayer temperatures rate of temperature fall are dropped to 25 ℃, thus at Si substrate large area deposition the number of plies inconsistent (the 1-3 layer does not wait) graphene film.Fig. 3 is the scanning electron microscope image at single crystalline Si Grown graphene film.
Effect: Si is the core material of contemporary silica-based electron device, numeral/logical circuit, directly at semiconducter substrate growing graphene films such as Si, will speed up the integrated of Graphene technology and contemporary optoelectronics industry, reduces cost.
The technological method that produces active atoms of carbon or carbonaceous active group is the energy particle technological method, includes but not limited to radio frequency processing, laser treatment, electron beam treatment, neutron beam processing, Ion Beam Treatment, Cement Composite Treated by Plasma, microwave treatment, X ray processing, alpha-ray processing, β Irradiation, gamma-rays processing, UV treatment, infra red treatment or thermal radiation processing.Adopt in the present embodiment the electron beam that is produced by electron beam gun to come ionization C
2H
4, but also can adopt other energy particle technology to come ionization.
The substrate that is used for the growing graphene film can be to have the substrate of catalytic activity such as Ni, Pt, Co, Fe, Al, Cr, Cu, Mg, Mn, Rh, Ta, Ti, W, U, Zr, V, Pd, Ru, Ir, Re, TiC, HfC, WC, LaB
6Or a kind of or its arbitrary combination of polycrystalline copper, also can be not have the substrate of catalytic activity such as semi-conductor and isolator to comprise Si, GaN, Ge, ZnO, CuO, InAs, GaAs, SiO
2, Al
2O
3, HfO
2, BN, SiC, SiN
x, MgO, GeS, BaF
2, MgF
2, LaF
3, GaF
2, GaP, InP, LiF, InSb, BaTiO
3, LiNbO
3, LaAlO
3, NdGaO
3, SrTiO
3, LaAlO
3, LiGaO
2, LiTaO
3, YAlO
3, YVO
4, ZnS, ZnSe, ZnTe, sapphire, mica, polymer poly ethylene glycol terephthalate (PET) etc.; Graphene film is to synthesize not have on the single crystalline Si substrate of catalysis in the present embodiment.
Embodiment 2: prepare graphene film at polymer poly ethylene glycol terephthalate (PET) substrate
May further comprise the steps: import the PET substrate into supervacuum chamber, the PET underlayer temperature is 150 ℃, and toward the supervacuum chamber ventilating methane, and maintenance air pressure is 8 * 10
-4Torr, adopt ion gun with acceleration voltage 1keV ionization methane, the methane of ionization is deposited on the PET substrate like this, depositing time is 5min, then when temperature is 100 ℃, sample is carried out the 60min anneal and has synthesized the graphene film that thickness is about 33.5nm (l00 layer) at PET.
Effect: various flat pannel display, touch-screen and solar cell etc. all need ELD, flexible device is more and more attracted attention, PET is transparent flexible materials, Graphene that directly will transparent conduction under lower temperature is grown on the PET, lays a good foundation for developing soft graphite alkene conductive, transparent membrane technique.
The technological method that produces active atoms of carbon or carbonaceous active group is the energy particle technological method, includes but not limited to radio frequency processing, laser treatment, electron beam treatment, neutron beam processing, Ion Beam Treatment, Cement Composite Treated by Plasma, microwave treatment, X ray processing, alpha-ray processing, β Irradiation, gamma-rays processing, UV treatment, infra red treatment or thermal radiation processing.Adopt in the present embodiment ion gun to come ionization methane, but also can adopt other energy particle technology to come ionization.
The substrate that is used for the growing graphene film can be to have the substrate of catalytic activity such as Ni, Pt, Co, Fe, Al, Cr, Cu, Mg, Mn, Rh, Ta, Ti, W, U, Zr, V, Pd, Ru, Ir, Re, TiC, HfC, WC, LaB
6Or a kind of or its arbitrary combination of polycrystalline copper, also can be not have the substrate of catalytic activity such as semi-conductor and isolator to comprise Si, GaN, Ge, ZnO, CuO, InAs, GaAs, SiO
2, Al
2O
3, HfO
2, BN, SiC, SiN
x, MgO, GeS, BaF
2, MgF
2, LaF
3, GaF
2, GaP, InP, LiF, InSb, BaTiO
3, LiNbO
3, LaAlO
3, NdGaO
3, SrTiO
3, LaAlO
3, LiGaO
2, LiTaO
3, YAlO
3, YVO
4, ZnS, ZnSe, ZnTe, sapphire, mica, polymer poly ethylene glycol terephthalate (PET) etc.; To be about the graphene film of 33.5nm be to synthesize not have on the insulating material PET of catalysis to thickness in the present embodiment.
Embodiment 3: at polycrystalline copper substrate growing graphene film
May further comprise the steps: be that the polycrystalline copper sheet of 25 μ m carries out mechanical polishing with thickness, spin coating thickness is the polymethylmethacrylate (PMMA) of 100nm on the Cu sheet after the polishing, yet passes to high vacuum chamber (2 * 10
-5Torr), adopt radio frequency beam with the PMMA ionization, simultaneously underlayer temperature is risen to 1050 ℃ and keep 10min, at last with near 25 ℃ and synthesized single-layer graphene at whole polycrystalline copper substrate of underlayer temperature.Fig. 4 is that the single-layer graphene that is synthesized is transferred to SiO
2Auger electron collection of illustrative plates on the substrate.
Effect: the technological method that produces active atoms of carbon or carbonaceous active group is the energy particle technological method, includes but not limited to radio frequency processing, laser treatment, electron beam treatment, neutron beam processing, Ion Beam Treatment, Cement Composite Treated by Plasma, microwave treatment, X ray processing, alpha-ray processing, β Irradiation, gamma-rays processing, UV treatment, infra red treatment or thermal radiation processing.Adopt in the present embodiment radio frequency source to produce plasma body and come the solid-state PMMA of ionization, but also can adopt other energy particle technology to come ionization.
The substrate that is used for the growing graphene film can be to have the substrate of catalytic activity such as Ni, Pt, Co, Fe, Al, Cr, Cu, Mg, Mn, Rh, Ta, Ti, W, U, Zr, V, Pd, Ru, Ir, Re, TiC, HfC, WC, LaB
6Or a kind of or its arbitrary combination of polycrystalline copper, also can be not have the substrate of catalytic activity such as semi-conductor and isolator to comprise Si, GaN, Ge, ZnO, CuO, InAs, GaAs, SiO
2, Al
2O
3, HfO
2, BN, SiC, SiN
x, MgO, GeS, BaF
2, MgF
2, LaF
3, GaF
2, GaP, InP, LiF, InSb, BaTiO
3, LiNbO
3, LaAlO
3, NdGaO
3, SrTiO
3, LaAlO
3, LiGaO
2, LiTaO
3, YAlO
3, YVO
4, ZnS, ZnSe, ZnTe, sapphire, mica, polymer poly ethylene glycol terephthalate (PET) etc.; To be grown on the polycrystalline copper substrate with catalytic activity at the present embodiment single-layer graphene.
Embodiment 4: at monocrystalline Ni (111) substrate growing graphene film
May further comprise the steps: the temperature of regulating mica substrate is 400 ℃, adopts vacuum heat deposition at the thick Ni film of mica deposition 100nm, carries out 500 ℃ of thermal treatment 2h after the Ni thin film deposition again, thereby must be at the mica Ni (111) that grown; Ni (111) substrate of growth is passed to supervacuum chamber, and regulating underlayer temperature is 900 ℃, and toward the supervacuum chamber ventilating methane, and maintenance air pressure is 2 * 10
-4Torr adopts microwave with the methane ionization and deposits to 20min on Ni (111) substrate, at last double-layer graphite alkene with the rapid near room temperature of underlayer temperature and on whole Ni (111) substrate.
Effect: the technological method that produces active atoms of carbon or carbonaceous active group is the energy particle technological method, includes but not limited to radio frequency processing, laser treatment, electron beam treatment, neutron beam processing, Ion Beam Treatment, Cement Composite Treated by Plasma, microwave treatment, X ray processing, alpha-ray processing, β Irradiation, gamma-rays processing, UV treatment, infra red treatment or thermal radiation processing.Adopt in the present embodiment microwave to come ionization methane, but also can adopt other energy particle technology to come ionization.
The substrate that is used for the growing graphene film can be to have the substrate of catalytic activity such as Ni, Pt, Co, Fe, Al, Cr, Cu, Mg, Mn, Rh, Ta, Ti, W, U, Zr, V, Pd, Ru, Ir, Re, TiC, HfC, WC, LaB
6Or a kind of or its arbitrary combination of polycrystalline copper, also can be not have the substrate of catalytic activity such as semi-conductor and isolator to comprise Si, GaN, Ge, ZnO, CuO, InAs, GaAs, SiO
2, Al
2O
3, HfO
2, BN, SiC, SiN
x, MgO, GeS, BaF
2, MgF
2, LaF
3, GaF
2, GaP, InP, LiF, InSb, BaTiO
3, LiNbO
3, LaAlO
3, NdGaO
3, SrTiO
3, LaAlO
3, LiGaO
2, LiTaO
3, YAlO
3, YVO
4, ZnS, ZnSe, ZnTe, sapphire, mica, polymer poly ethylene glycol terephthalate (PET) etc.; Double-layer graphite alkene is to be grown on monocrystalline Ni (111) substrate with catalytic activity in the present embodiment.
Embodiment 5: at SiO
2The Grown graphene film
May further comprise the steps: adopt photoetching and caustic solution at SiO
2It is 100nm that the surface forms width, and thickness is the bar paten of 0.5nm; With figuratum Si/SiO
2Substrate is sent to silica tube, reaches high vacuum, and heating makes underlayer temperature reach 800 ℃; Make liquid ethanol vaporization and process laser treatment produce the active group of carbon containing, then take Ar as carrier the carbonaceous active group is imported silica tube at Si/SiO
2Upper growing graphene film behind the growth 5min, is down to 25 ℃ with underlayer temperature with 30 ℃/minute speed, thereby at SiO
2The surface obtains the graphene film that thickness is about 3.35nm (10 layers).
Effect: SiO
2The important dielectric materials of contemporary silica-based electron device, numeral/logical circuit, directly at SiO
2Insulating substrate growing graphene film will speed up the integrated of Graphene technology and contemporary optoelectronics industry, reduces cost.
The technological method that produces active atoms of carbon or carbonaceous active group is the energy particle technological method, includes but not limited to radio frequency processing, laser treatment, electron beam treatment, neutron beam processing, Ion Beam Treatment, Cement Composite Treated by Plasma, microwave treatment, X ray processing, alpha-ray processing, β Irradiation, gamma-rays processing, UV treatment, infra red treatment or thermal radiation processing.Adopt in the present embodiment laser to come the ionization liquid ethanol, but also can adopt other energy particle technology to come ionization.
The substrate that is used for the growing graphene film can be to have the substrate of catalytic activity such as Ni, Pt, Co, Fe, Al, Cr, Cu, Mg, Mn, Rh, Ta, Ti, W, U, Zr, V, Pd, Ru, Ir, Re, TiC, HfC, WC, LaB
6Or a kind of or its arbitrary combination of polycrystalline copper, also can be not have the substrate of catalytic activity such as semi-conductor and isolator to comprise Si, GaN, Ge, ZnO, CuO, InAs, GaAs, SiO
2, Al
2O
3, HfO
2, BN, SiC, SiN
x, MgO, GeS, BaF
2, MgF
2, LaF
3, GaF
2, GaP, InP, LiF, InSb, BaTiO
3, LiNbO
3, LaAlO
3, NdGaO
3, SrTiO
3, LaAlO
3, LiGaO
2, LiTaO
3, YAlO
3, YVO
4, ZnS, ZnSe, ZnTe, sapphire, mica, polymer poly ethylene glycol terephthalate (PET) etc.; Thickness is that the graphene film of 3.35nm synthesizes the SiO in the insulation that does not have catalysis in the present embodiment
2On the substrate.
Above-described embodiment only is not used in for explanation the present invention and limits the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (6)
1. the method for a synthesizing graphite alkene film is characterized in that comprising the steps:
1) adopt the energy particle technological method from the solid-state carbon source, liquid carbon source, gaseous carbon source material or the aforementioned carbon source that contain carbon, to produce active atoms of carbon or carbonaceous active group in two or more mixed carbon source material arbitrarily;
2) active atoms of carbon that produces or carbonaceous active group are deposited on the substrate with catalytic activity or have on the substrate of catalytic activity and form graphene film.
2. the method for synthesizing graphite alkene film according to claim 1 is characterized in that described energy particle technological method comprises radio frequency processing, laser treatment, electron beam treatment, neutron beam processing, Ion Beam Treatment, Cement Composite Treated by Plasma, microwave treatment, Irradiation, UV treatment or infra red treatment.
3. the method for synthesizing graphite alkene film according to claim 1 is characterized in that the described substrate that does not have catalytic activity comprises semi-conductor or insulating material.
4. the method for synthesizing graphite alkene film according to claim 1 is characterized in that described substrate with catalytic activity comprises Ni, Pt, Co, Fe, Al, Cr, Mg, Mn, Rh, Ta, Ti, W, U, Zr, V, Pd, Ru, Ir, Re, TiC, HfC, WC, LaB
6Or a kind of or its arbitrary combination of polycrystalline copper.
5. the method for synthesizing graphite alkene film according to claim 1 is characterized in that described active atoms of carbon refers to form the carbon atom of Graphene; Described carbonaceous active group refers to the group with carbonium ion or carbanion.
6. the method for synthesizing graphite alkene film according to claim 1 is characterized in that the number of plies of the graphene film that forms at described substrate is 1 layer to 100 layers, is preferably 1 layer to 10 layers, and optimum is 1 layer to 3 layers.
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